U.S. patent number 5,578,419 [Application Number 08/223,605] was granted by the patent office on 1996-11-26 for dyes for color filters, and photosensitive resist resin composition containing the same.
This patent grant is currently assigned to Mitsui Toatsu Chemicals, Incorporated. Invention is credited to Hisato Itoh, Akio Karasawa, Kenichi Sugimoto.
United States Patent |
5,578,419 |
Itoh , et al. |
November 26, 1996 |
Dyes for color filters, and photosensitive resist resin composition
containing the same
Abstract
Dyes suitable for use in the fabrication of color filters are
described which contain one or more photopolymerizable substituents
preferably represented by the following formula: where D represents
a chromphoric nucleus, A denotes a connecting group, Y means the
photopolymerizable group, n.sup.1 is 1-10,000, and n.sup.2 stands
for an integer of 1-10. Also described are photosensitive resist
resin compositions containing the dyes as well as color filters
fabricated by curing the photosensitive resist resin
compositions.
Inventors: |
Itoh; Hisato (Yokohama,
JP), Karasawa; Akio (Zushi, JP), Sugimoto;
Kenichi (Yokohama, JP) |
Assignee: |
Mitsui Toatsu Chemicals,
Incorporated (Tokyo, JP)
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Family
ID: |
26572886 |
Appl.
No.: |
08/223,605 |
Filed: |
April 6, 1994 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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987960 |
Dec 11, 1992 |
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Foreign Application Priority Data
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Dec 12, 1991 [JP] |
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3-328474 |
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Current U.S.
Class: |
430/281.1; 8/677;
8/647; 546/347; 548/548; 548/546; 552/242; 552/226; 522/904;
522/48; 8/679; 552/223; 430/7; 8/678 |
Current CPC
Class: |
C09B
69/109 (20130101); G03F 7/0007 (20130101); G03F
7/027 (20130101); C09B 69/10 (20130101); Y10S
522/904 (20130101) |
Current International
Class: |
C09B
69/00 (20060101); C09B 69/10 (20060101); G03F
7/00 (20060101); G03F 7/027 (20060101); C09B
001/16 (); C09B 062/004 () |
Field of
Search: |
;552/242,223,226
;548/545,546,547,548,426
;430/495,287,915,920,281,7,288,495.1,287.1,281.1,288.1
;522/48,63,904 ;546/347 ;8/507,647,677,678,679 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0098522 |
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Jan 1984 |
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EP |
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0168694 |
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Jan 1986 |
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EP |
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0300770 |
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Jan 1989 |
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EP |
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0359934 |
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Mar 1990 |
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EP |
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0371398 |
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Jun 1990 |
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EP |
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2038849 |
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Jul 1980 |
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GB |
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Other References
Leznoff et al., "Phthalocyanines Properties and Applications", VCH
Verlagsgesellchaft, 1989, pp. 6-13, 28, 40-44, and 116..
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Primary Examiner: McPherson; John A.
Attorney, Agent or Firm: Millen, White, Zelano &
Branigan, P.C.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No.
07/987,960, filed Dec. 11, 1992, now abandoned.
Claims
What is claimed is:
1. A dye represented by formula ( 1):
wherein D is an anthraquinone nucleus represented by any one of
formulae (i) to (iii): ##STR199## wherein X is an oxygen or sulfur
atom, R'.sup.1 to R'.sup.4 each are independently a hydrogen atom,
a substituted or unsubstituted alkyl group, a substituted or
unsubstituted alkoxy group or a halogen atom; ##STR200## wherein
R'.sup.5 to R'.sup.8 each are independently a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aryl group or a
hydrogen atom, R'.sup.9 to R'.sup.12 each are independently a
hydrogen atom, substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkoxy group or a halogen atom;
##STR201## wherein R'.sup.13 to R'.sup.18 each are independently a
hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkoxy group or a halogen atom,
R'.sup.19 to R'.sup.22 each are independently a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted aryl
group or a hydrogen atom;
A is a connecting group of one of the following formulae (19) to
(22), in which parenthesized recurring units may be combined
together at random: ##STR202## wherein one of R.sup.26 and R.sup.27
represents a hydrogen atom and the other denotes a hydroxyl group;
and r.sup.1 and s.sup.1 each stands for an integer of from 1-10000;
##STR203## wherein R.sup.28 to R.sup.31 independently represent a
hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted cycloalkyl group, a substituted or
unsubstituted aryl group, or a halogen atom, and r.sup.2 stands for
an integer of from 1-10000; ##STR204## wherein r.sup.3 stands for
an integer of 1-10000; ##STR205## wherein R.sup.32 to R.sup.37
independently represent a hydrogen atom, a halogen atom, a hydroxyl
group, --SH, an amino group, a substituted or unsubstituted alkyl
group, a substituted or unsubstituted cycloalkyl group, a
substituted or unsubstituted aryl group, a substituted or
unsubstituted alkoxyl group, a substituted or unsubstituted
aryloxyl group, a substituted or unsubstituted alkylamino group, or
a substituted or unsubstituted arylamino group; and a.sup.1,
b.sup.1 and c.sup.1 each stands for an integer of from 0-10000,
Y is a photopolymerizable group represented by any one of formulae
(2) to (7) ##STR206## wherein R.sup.1 to R.sup.4 independently
represent a substituted or unsubstituted alkyl group, a substituted
or unsubstituted cycloalkyl group, a substituted or unsubstituted
aralkyl group or a hydrogen atom, R.sup.5 denotes a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aryl group, a
substituted or unsubstituted aralkyl group or a hydrogen atom,
R.sup.5' is a hydrogen atom or methyl group, provided that if
R.sup.5' is a methyl group, then R.sup.5 is a hydrogen atom, and
R.sup.6 to R.sup.8 independently mean a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted alkoxyl group, a
halogen atom or a hydrogen atom,
n.sup.1 is 1-10,000, and n.sup.2 is an integer from 1 to 10,
wherein, a substituted alkyl means alkyl substituted by alkoxy,
halogen or hydroxyl groups; substituted cycloalkyl means cycloalkyl
substituted by alkyl,alkoxy, halogen, cyano, nitro and/or hydroxyl
groups; substituted alkoxyl means alkoxyl substituted by alkoxy,
halogen or hydroxy groups; substituted aryl means aryl substituted
by alkyl, alkoxy or halogen groups; substituted aralkyl means
aralkyl substituted by alkyl, alkoxy or halogen groups; substituted
alkylamino means alkylamino substituted by alkoxy, halogen or
hydroxyl groups; and substituted arylamino means arylamino
substituted by alkyl, alkoxy or halogen groups.
2. The dye of claim 1, wherein n.sup.2 is an integer from 1-4.
3. The dye of claim 1, wherein n.sup.1 and n.sup.2 are each 1.
4. The dye of claim 1, wherein the photopolymerizable group
represented by Y is selected from the group consisting of the
following formulae (2) and (4) to (7) ##STR207## wherein R.sup.1
represents a substituted or unsubstituted alkyl group, a
substituted or unsubstituted cycloalkyl group, a substituted or
unsubstituted aralkyl group or a hydrogen atom, R.sup.5 denotes a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted aralkyl group or a hydrogen
atom, and R.sup.6 to R.sup.8 independently mean a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted alkoxyl group,a
halogen atom or a hydrogen atom.
5. A dye of claim 1, wherein D of formula 1 is an anthraquinone
nucleus represented by formula (i).
6. A dye of claim 1, wherein D of formula 1 is an anthraquinone
nucleus represented by formula (ii).
7. A dye of claim 1, wherein D of formula 1 is an anthraquinone
nucleus represented by formula (iii).
8. A dye of claim 1, wherein D of formula 1 is an anthraquinone
nucleus represented by formula (i) in which R'.sup.1, R'.sup.2 and
R'.sup.4 each are a hydrogen atom; R'.sup.3 is a methyl group; "X"
is an oxygen atom; "A" is methylene attached to the benzene ring
bearing the R'.sup.3 methyl group; "Y" is a compound of formula (7)
in which R.sup.8 is a hydrogen atom; and "n.sup.1 " and "n.sup.2 "
each are the integer "1".
9. A dye formulation adapted for use as a color filter comprising a
dye of claim 1, in admixture with a film forming substrate
comprising a photosensitive resin having at least one
photopolymerizable substituent.
10. The dye formulation of claim 9, wherein n.sup.2 is an integer
from 1-4.
11. The dye formulation of claim 9, wherein n.sup.1 and n.sup.2 are
each 1.
12. The dye formulation of claim 9, wherein the photopolymerizable
group represented by Y is selected from the group consisting of the
following formulae (2), (3), (5), (6) and (7) ##STR208## wherein
R.sup.1 to R.sup.4 independently represent a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aralkyl group or a
hydrogen atom, and R.sup.6 to R.sup.8 independently mean a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted
alkoxyl group,a halogen atom or a hydrogen atom.
13. A dye formulation of claim 9, wherein D of formula 1 of the dye
therein is an anthraquinone nucleus represented by formula (i).
14. A dye formulation of claim 9, wherein D of formula 1 of the dye
therein is an anthraquinone nucleus represented by formula
(ii).
15. A dye formulation of claim 9, wherein D of formula 1 of the dye
therein is an anthraquinone nucleus represented by formula (iii).
Description
BACKGROUND OF THE INVENTION
1) Field of the Invention
This invention relates to dyes for color filters suitable for use
in liquid crystal television sets, color image pickup tubes and
color copying machines, photosensitive resist resin compositions
containing the dyes, and color filters fabricated by curing the
resin compositions.
2) Related Art of the Invention
Known fabrication processes of color filters include printing
processes utilizing the principle of printing, dyeing processes and
pigment printing processes, both making use of photolithography,
and electrodeposition processes involving electrochemical
deposition of a dye ("Nikkei New Material", 48-56 (Feb. 25,
1991)).
Fabrication of a filter by a dyeing process comprises, as shown in
FIG. 1 by way of example, the following steps: (1) coating a glass
substrate with a coating formulation which is formed of a
water-soluble dyeable high-molecular material, such as gelatin or
casein, and to which has been imparted photosensitivity by the
addition of a bichromate, (2) exposing the thus-formed coating to
ultraviolet rays through a photomask, (3) developing the
thus-exposed coating to form a pattern, (4) coloring the pattern
with an acid dye, (5) subjecting the thus-colored pattern to
color-mixing protection, and (6) repeating steps (1) to (5) until
the other two colors are applied to the glass substrate. The color
filter obtained by the dyeing process has excellent pattern
resolution and dimensional accuracy, superb light transmission and
high lightness. Such a dyeing process is, however, accompanied by
the following drawbacks:
(1) If the glass substrate is dyed with the second color without
applying color protection subsequent to its coloration with the
first color, the dye for the second color migrates into the filter
layer of the first color so that the spectral characteristics are
deteriorated. To avoid this problem, it is necessary to apply a
color protection film with an acryl, urethane or epoxy resin or to
subject the surface of the dyed medium to chemical treatment with
tannic acid or the like.
(2) The heat resistance is insufficient due to the use of gelatin
or casein as the base of the photosensitive resin.
On the other hand, fabrication of a filter by a pigment printing
process makes use of a pigment which is employed for heat-resistant
paints or for the coloration of plastics, and as depicted in FIG. 2
by way of example, comprises the following steps: (1) coating a
glass substrate with a photosensitive resin containing a pigment
uniformly dispersed therein, (2) exposing the thus-coated glass
substrate to ultraviolet rays, (3) developing the thus-exposed
coating to form a colored-pattern, and (4) repeating the steps (1)
to (3) until the other two colors are applied to the glass
substrate. The color filter obtained by the pigment printing
process has pattern accuracy as high as that obtained by the dyeing
process and is also excellent in heat resistance and light
resistance, but is accompanied by the following drawbacks:
(1) Its light transmission is inferior and its contrast is low,
because light is scattered by the pigment particles.
(2) Prior to coating the photosensitive resin in which the pigment
is uniformly dispersed, the resin should be passed through a filter
to eliminate dust and large particles. Processing troubles
therefore occur including clogging of the filter by coagulated
pigment particles.
If the process shown in FIG. 2 is followed to fabricate a filter by
using "M/P Pink REL" (trade name; product of Mitsui Toatsu Dyes,
Ltd.) or "PS Green B" (trade name; product of Mitsui Toatsu Dyes,
Ltd.), a resin-soluble conventional dye, instead of a pigment, the
conventional dye is not immobilized in a matrix because its
molecular weight is lower than 500. As a consequence, the dye may
move to an adjacent matrix and cause color mixing. Further, the
solubility of the conventional dye is insufficient so that the
color filter must have a great film thickness in order to obtain a
desired color density.
It is conceivable to immobilize a dye in a matrix resin using, as
the dye, a reactive dye containing a monochlorotriazinyl group or a
sulfatoethylsulfone group. Such reactive groups are however of the
heat reactive type, thereby making it extremely difficult to
fabricate micro-matrices like color filters. In addition, a salt
remains in the resin after the reaction so that the electrical
insulating property is impaired.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a novel dye for a
color filter, which is free of problems such as the above-mentioned
filter clogging, requires no treatment for the prevention of mixing
of individual colors and can furnish a color filter which has good
transmission characteristics and is excellent in durability such as
heat resistance, light resistance and moistureproofness.
Another object of the present invention is to provide a
photosensitive resist resin composition containing the
above-described novel dye for a color filter.
A further object of the present invention is to provide a color
filter having good transmission characteristics and excellent
durability such as heat resistance, light resistance and
moistureproofness.
To attain the above objects, the present inventors have proceeded
with an extensive investigation. As a result, it has been found
that a dye meeting at least one of the below-described two
requirements can be stably immobilized in a filter matrix and can
hence provide a color filter free of dye color mixing and excellent
in transmission characteristics and durability. These requirements
are:
(1) Possession of a photopolymerizable substituent; and
(2) Molecular weight of at least 500 but not greater than 4000.
Use of a dye capable of satisfying at least either one of these
requirements makes it possible to stably immobilize the dye in a
filter matrix.
The present invention therefore provides dyes represented by the
below-described formula (1),
wherein D represents a chromophoric nucleus, A denotes a connecting
group, Y means the photopolymerizable group, .sub.n.spsb.1 is
1-10000, and .sub.n.spsb.2 stands for an integer of 1-10.
The present invention also provides dyes having a molecular weight
of at least 500 but not greater than 4000 and represented by the
below-described formula (8) or (9),
wherein D in each formula represents a chromophoric nucleus, and B
and E each denotes a connecting group, Z is --COOR.sup.9,
CONR.sup.10 R.sup.11, --OCOR.sup.12, --OCOOR.sup.13,
--OCONHR.sup.14, --NHR.sup.15 or --NR.sup.16 R.sup.17, R.sup.9 and
R.sup.12 to R.sup.17 independently representing a substituted or
unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aryl group or a
substituted or unsubstituted aralkyl group and R.sup.10 and
R.sup.11 independently representing a substituted or unsubstituted
alkyl group, a substituted or unsubstituted cycloalkyl group, a
substituted or unsubstituted aryl group, a substituted or
unsubstituted. aralkyl group or a hydrogen atom, and m stands for
an integer of 1-10.
The present invention also provides photosensitive resist resin
compositions comprising the aforesaid dyes, and LCD color filters
fabricated by curing the photosensitive resist resin
compositions.
The dyes according to the present invention are suitable as dyes
for color filters for the following reasons:
(1) The dyes according to this invention are soluble in a resin.
Especially, the dyes containing one or more ester, amido, acyl,
carbamoyl, amino and/or like groups in their molecules have
excellent compatibility with a resin so that they do not develop
clogging or coating irregularities when they are coated upon
fabrication of color filters having red, green and blue matrices
with a photosensitive resist resin.
(2) The dyes according to this invention contain one or more
photopolymerizable substituents. Upon photo-setting a resist resin
composition, each dye and a photosensitive resist resin are
copolymerized or polymerization takes place between molecules of
each dye so that the dye is immobilized in the resin matrix. In the
case of each dye having a high molecular weight of at least 500 but
not greater than 4000, it does not migrate of a resin matrix once
it enters the resin matrix and is incorporated therein. As a
consequence, it is possible to avoid color mixing that may
otherwise take place due to migration of the dye into an adjacent
layer of a different color.
(3) As the dyes according to this invention are each immobilized in
a matrix, the resulting color filter is free from discoloration
which may otherwise take place as a result of sublimation of the
dye, and is also excellent in durability such as heat resistance
and moistureproofness.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross-section showing fabrication steps of a
color filter according to a conventional dyeing process;
FIG. 2 is a schematic cross-section illustrating fabrication steps
of a color filter according to a conventional pigment printing
process; and
FIGS. 3 through 6 are cross-sections depicting fabrication steps of
a color filter according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "polymerizable substituents" as used herein means groups
capable of inducing copolymerization between a resin and a dye or
between dyes under light as well as photosensitive groups used in
photosensitive resist resins disclosed in the literature (for
example, "Photopolymer Handbook" compiled by Photo Polymer
Association and published by Kogyo Chosakai, 1989). It includes
those employed to bond dye molecules in a pendant-like form from
resin molecules.
Preferred examples of dyes bonded thereon according to the present
invention with photosensitive polymerizable substituents include
those represented by the formula (1). In addition, it is preferred
that the photosensitive group represented by Y in the formula (1)
is selected from the group consisting of the following formulas
(2)-(7): ##STR1## wherein R.sup.1 to R.sup.4 independently
represent a substituted or unsubstituted alkyl group, a substituted
or unsubstituted cycloalkyl group, a substituted or unsubstituted
aralkyl group, or a hydrogen atom; R.sup.5 represents a substituted
or substituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aryl group, or a
substituted or unsubstituted aralkyl group, or a hydrogen atom;
R.sup.5' is a hydrogen atom or a methyl group, provided that if
R.sup.5' is a methyl group, then R.sup.5 is a hydrogen atom; and
R.sup.6, R.sup.7 and R.sup.8 independently represent a substituted
or unsubstituted alkyl group, a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted alkoxy group, a
halogen atom, or a hydrogen atom.
It is preferred that if Y is formula (4), then D is the
quinophthalone nucleus, the anthraquinone nucleus represented by
any one of formula (i) to (III), (VII) and (VIII) or a
phthalocyanine nucleus represented by formula (ix) ##STR2## wherein
R'.sup.58 is a substituted or unsubstituted alkyl group, a
substituted or unsubstituted aryl group or a substituted or
unsubstituted aralkyl group, Met is a divalent metal, a trivalent
mono-substituted metal, a tetravalent di-substituted metal or a
metal oxide, and Z is a hydrogen or halogen atom.
In the formulas (2) to (8), examples of the unsubstituted alkyl
group include linear and branched alkyl groups such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl,
n-pentyl, iso-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl,
n-dodecyl, 2-methylbutyl, 2-methylpentyl, 1,3-dimethylbutyl,
1-iso-propylpropyl, 1,2-dimethylbutyl, n-heptyl,
1,4-dimethylpentyl, 2-methyl-1-iso-propylpropyl,
1-ethyl-3-methylbutyl, n-octyl, 2-ethythexyl,
2-methyl-1-iso-propylbutyl,
2,2-dimethyl-1-iso-propyl-1-t-butylpropyl, and n-nonyl. Exemplary
substituted alkyl groups include alkoxyalkyl groups-such as
methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl,
butoxyethyl, .gamma.-methoxypropyl, .gamma.-ethoxypropyl,
methoxyethoxyethyl, ethoxyethoxyethyl, dimethoxymethyl,
diethoxymethyl, dimethoxyethyl, and diethoxyethyl; halogenated
alkyl groups such as chloromethyl, 2,2,2-trichloroethyl,
trifluoromethyl, and 1,1,1,3,3,3-hexafluoro-2-propyl; and
hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl,
hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyoctyl.
Examples of the unsubstituted cycloalkyl group include cyclopentyl
and cyclohexyl. Exemplary substituted cycloalkyl groups include
cyclopentyl and cyclohexyl groups substituted by one or more
groups, for example, alkyl groups such as methyl, ethyl and propyl,
alkoxy groups such as methoxy, ethoxy and butoxy, halogen atoms
such as chlorine, bromine, fluorine and iodine, cyano groups, nitro
groups and/or hydroxyl groups.
Examples of the unsubstituted alkoxyl group include methoxyl,
ethoxyl, n-propoxyl, iso-propoxyl, n-butoxyl, iso-butoxyl,
sec-butoxyl, t-butoxyl, n-pentoxyl, iso-pentoxyl, neo-pentoxyl,
1,2-dimethylpropoxyl, n-hexyloxyl, cyclohexyloxyl,
1,3-dimethylbutoxyl, 1-iso-propylpropoxyl, 1,2-dimethylbutoxyl,
n-heptyloxyl, 1,4-dimethylpentyloxyl, 2-methyl-1-isopropylpropoxyl,
1-ethyl-3-methylbutoxyl, n-octyloxyl, 2-ethylhexyloxyl,
3-methyl-1-iso-propylbutoxyl, 2-methyl-1-iso-propylbutoxy,
1-t-butyl-2-methylpropoxyl, n-nonyloxyl and n-decyloxyl. Exemplary
substituted alkoxyl groups include alkoxyalkoxyl groups such as
methoxymethoxyl, methoxyethoxyl, ethoxyethoxyl, propoxyethoxyl,
butoxyethoxyl, .gamma.-methoxypropoxyl, .gamma.-ethoxypropoxyl,
methoxyethoxyethoxyl, ethoxyethoxyethoxyl, dimethoxymethoxyl,
diethoxymethoxyl, dimethoxyethoxyl, and diethoxyethoxyl;
halogenated alkoxyl groups such as chloromethoxyl,
2,2,2-trichloroethoxyl, trifluoromethoxyl, and
1,1,1,3,3,3-hexafluoro-2-propoxyl; and hydroxyalkoxyl groups such
as hydroxymethoxyl, hydroxyethoxyl, hydroxypropoxyl,
hydroxybutoxyl, hydroxypentyloxyl, and hydroxyoctyloxyl.
Illustrative of the unsubstituted aryl group include phenyl,
naphthyl and indenyl.
Examples of the substituted aryl group include phenyl, naphthyl and
indenyl groups containing one or more substituents, for example,
linear and branched alkyl groups such as methyl, ethyl, propyl,
iso-propyl, butyl, 2-methylpropyl, pentyl and/or neo-pentyl,
alkoxyl groups such as methoxyl, ethoxyl and/or propoxyl and/or
halogen atoms such as chlorine, fluorine, bromine and/or
iodine.
Examples of the unsubstituted aralkyl group include benzyl and
phenethyl.
Illustrative of the substituted aralkyl group include benzyl and
phenetyl groups containing one or more substituents, for example,
linear and branched alkyl groups such as methyl, ethyl, propyl,
iso-propyl, butyl, 2-methylpropyl, pentyl and/or neo-pentyl,
alkoxyl groups such as methoxyl, ethoxyl and/or propoxyl, and/or
halogen atoms such as chlorine, fluorine, bromine and/or
iodine.
Exemplary halogen atoms include chlorine, bromine, iodine and
fluorine.
In the formulas (1), (8) and (9), any known skeletons disclosed in
literature can be used as the chromophoric nucleus represented by
D, including azo, anthraquinone, phthalocyanine, quinophthalone
styrylic, indeaniline and cyanine skeletons (see, for example,
"Color Handbook", compiled by Ohkawara et al., Kodansha Ltd (1986),
"The Chemistry of Synthetic Dyes", Vols I-VI, edited by K.
Venkataraman et al. and published by Academic Press, and "Synthetic
Dye Overview" written by Hiroshi Horiguchi, Sankyo Publishing Co.
The skeletons will hereinafter be described specifically. They can
contain one or more substituents thereon. Each connecting group in
the formulas (1), (8) and (9) can bond to a substituent which has
been bonded to a chromophoric nucleus. ##STR3##
Particularly preferred, illustrative chromophoric nuclei include,
from the viewpoint of durability, dye skeletons represented by the
following formulas (16) to (18): ##STR4## wherein Y.sup.1
represents 1-15 same or different substituents selected from
hydrogen atoms, substituted and unsubstituted alkyl groups,
substituted and unsubstituted cycloalkyl groups, substituted and
unsubstituted aryl groups, substituted or unsubstituted alkoxyl
groups, substituted and unsubstituted aryloxyl groups, substituted
and unsubstituted alkylthio groups, substituted and unsubstituted
arylthio groups, substituted and unsubstituted alkylamino groups,
substituted and unsubstituted dialkylamino groups, substituted and
unsubstituted arylamino groups, substituted and unsubstituted
diarylamino groups, amino groups, halogen atoms, nitro group,
nitrile group, substituted and unsubstituted acyl groups,
substituted and unsubstituted alkoxycarbonyl groups, and
substituted and unsubstituted amido groups; Met is a divalent
metal, a trivalent mono-substituted metal, a tetravalent
di-substituted metal, or a metal oxide; and l stands for an integer
from 1-15; ##STR5## wherein Y.sup.2 represents 1-7 same or
different substituents selected from hydrogen atoms, substituted
and unsubstituted alkyl groups, substituted and unsubstituted
cycloalkyl groups, substituted and unsubstituted aryl groups,
substituted and unsubstituted alkoxyl groups, substituted and
unsubstituted aryloxyl groups, substituted and unsubstituted
alkylthio groups, substituted and unsubstituted arylthio groups,
substituted and unsubstituted alkylamino groups, substituted and
unsubstituted dialkylamino groups, substituted and unsubstituted
arylamino groups, substituted and unsubstituted diarylamino groups,
hydroxy group, amino groups, halogen atoms, nitro group, nitrile
group, substituted or unsubstituted acyl groups, substituted and
unsubstituted alkoxycarbonyl groups, substituted or unsubstituted
2,3-dicarboxyimide groups, and substituted and unsubstituted amido
groups; and p stands for an integer of from 1-7; ##STR6## wherein
Y.sup.3 represents 1-8 same or different substituents selected from
hydrogen atoms, substituted and unsubstituted alkyl groups,
substituted and unsubstituted cycloalkyl groups, substituted and
unsubstituted aryl groups, substituted and unsubstituted alkoxyl
groups, substituted and unsubstituted aryloxyl groups, substituted
and unsubstituted alkylthio groups, substituted and unsubstituted
arylthio groups, substituted and unsubstituted alkylamino groups,
substituted and unsubstituted dialkylamino groups, substituted and
unsubstituted arylamino, substituted and unsubstituted diarylamino
groups, amino groups, halogen atoms, nitro group, nitrile group,
substituted and unsubstituted acyl groups, substituted and
unsubstituted alkoxycarbonyl groups, and substituted and
unsubstituted amido groups; and q stands for an integer of from
1-8.
Also preferred for the group D of formulae (1), (8) and (9) are
groups of the formula (i), (ii), (iii), (vii) and (viii) described
as follows: ##STR7## wherein X is an oxygen or sulfur atom,
R'.sup.1 to R'.sup.4 each are independently a hydrogen atom, a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted alkoxy group or a halogen atom; ##STR8## wherein X is
an oxygen or sulfur atom, R'.sup.5 to R'.sup.8 each are
independently a substituted or unsubstituted alkyl group, a
substituted or unsubstituted cycloalkyl group, a substituted or
unsubstituted aryl group or a hydrogen atom, R'.sup.9 to R'.sup.12
each are independently a hydrogen atom, substituted or
unsubstituted alkyl group, a substituted or unsubstituted alkoxy
group or a halogen atom; ##STR9## wherein X is an oxygen or sulfur
atom, R'.sup.13 to R'.sup.18 each are independently a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted alkoxy group or a halogen atom, R'.sup.19 to
R'.sup.22 each are independently a substituted or unsubstituted
cycloalkyl group, a substituted or unsubstituted aryl group or a
hydrogen atom; ##STR10## wherein R'.sup.47 to R'.sup.54 each are
independently a hydrogen atom, a substituted or unsubstituted alkyl
group, substituted or unsubstituted alkoxy group, a substituted or
unsubstituted cycloalkyl group or a halogen atom, R'.sup.55 and
R'.sup.56 each are independently a substituted or unsubstituted
alkyl group, a substituted or unsubstituted alkoxy group, a cyano
group, a halogen atom or a hydrogen atom; ##STR11## wherein
R'.sup.57 is a substituted or unsubstituted alkyl group or a
substituted or unsubstituted aryl group.
In formula (1), the connecting group represented by A can be any
connecting group which can covalently bond a chromophoric nucleus
or its substituent to photopolymerizable group Y. Alternatively, it
is possible to directly bond a chromophoric nucleus or its
substituent to photopolymerizable group Y without the connecting
group A. Examples of the connecting group A include those
represented by the following formulas (19) to (22), in which
parenthesized recurring units may be combined together at random:
##STR12## wherein one of R.sup.26 and R.sup.27 represents a
hydrogen atom and the other denotes a hydroxyl group; and r.sup.1
and s.sup.1 each stands for an integer Of from 1-10000; ##STR13##
wherein R.sup.28 to R.sup.31 independently represent a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted aryl
group, or a halogen atom; and r.sup.2 stands for an integer of from
1-10000; ##STR14## wherein r.sup.3 stands for an integer of
1-100000. ##STR15## wherein R.sup.32 to R.sup.37 independently
represent a hydrogen atom, a halogen atom, a hydroxyl group, --SH,
an amino group, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted cycloalkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted alkoxyl
group, a substituted or unsubstituted aryloxyl group, a substituted
or unsubstituted alkylamino group, or a substituted or
unsubstituted arylamino group; and a.sup.1, b.sup.1 and c.sup.1
each stands for an integer of from 0-10000.
The connecting group represented by B in the formula (8) can be any
divalent connecting group. Alternatively, it is possible to
directly bond a chromophoric nucleus to a substituent without the
connecting group B. Its examples include the groups represented by
formulas (20) to (22) in which r.sup.1 to r.sup.3, s.sup.1,
a.sup.1, b.sup.1 and c.sup.1 each stands for an integer of from
1-100. The connecting group represented by E in the formula (9) can
be any divalent connecting group. Its examples include
--F--OCO--G--COO--F--, --F--COO--G--OOC--F--,
--F--CONH--G--NHCO--F--, --F--OCONH--G--NHCOO--F-- and
--F--OCOO--G--OCOO--F--. F and G can be any divalent connecting
groups. Their examples include the groups represented by the
formulas (20) to (23) in which r.sup.1 to r.sup.3, s.sup.1,
a.sup.1, b.sup.1 and c.sup.1 each stands for an integer of from
1-100, and parenthesized recurring units may be combined together
at random.
Formula (23) connecting groups are those of the formula ##STR16##
wherein R.sup.38 to R.sup.49 independently represent a hydrogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted aryl
group, or a halogen atom; R.sup.50 and R.sup.51 independently
represent a hydrogen atom, a substituted or unsubstituted alkyl
group, a substituted or unsubstituted cycloalkyl group, a
substituted or unsubstituted aryl group, a substituted or
unsubstituted alkoxyl group, or a halogen atom; a.sup.2, b.sup.2,
c.sup.2, a.sup.3, b.sup.3 and c.sup.3 each stands for an integer of
from 0-100; and d stands for an integer of 1-5.
Each photosensitive resist resin composition according to the
present invention comprises at least one of the dyes of the present
invention and a resist resin containing photosensitive groups
therein. It may further contain a photopolymerization initiator, a
diluent, and one or more other additives.
The dyes represented by the formula (1) or (8) can each be
synthesized by one of the following processes:
(1) a process in which the connecting group is bonded to the
chromophoric nucleus D, followed by bonding of Y or Z;
(2) a process in which the connecting group is bonded to Y or Z,
followed by bonding to the chromophoric nucleus D;
(3) a process in which a chromophoric nucleus intermediate is
reacted to the connecting group or with a connecting group
containing Y or Z, followed by the construction of the
corresponding chromophoric nucleus. One of these processes can be
selected suitably depending on the combination of the chromophoric
nucleus D, the connecting group and the group Y or Z;
The dyes represented by the formula (9) can each be synthesized by
one of the following processes:
(1) a process in which the chromophoric nucleus D is reacted with
the connecting group E, which contains a bifunctional group, in an
amount of 0.5 equivalent or less to conduct dimerization;
(2) a process in which the connecting group E is bonded to the
chromophoric nucleus D, followed by the bonding of the chromophoric
nucleus D. One of these processes can be selected suitably
depending on the combination of the chromophoric nucleus D and the
connecting group E;
In the process of the present invention for the fabrication of a
Color filter, any photosensitive resist resin can be used in
combination with the dye of the present invention as long as the
resin is curable by light. Namely, any resin containing one or more
photosensitive groups and which is known in the literature can be
used (see "Recording Materials and Photosensitive Resins",
published by the Publication Center of the Japan Society for the
Promotion of Science; and "Photopolymer Handbook", compiled by
Photopolymer Association and published by Kogyo Chosakai, 1989).
Preferred are resist resins containing photosensitive groups
selected from the-group consisting of the following formulas (10)
to (15): ##STR17## wherein R.sup.18 to R.sup.21 independently
represent a substituted or unsubstituted alkyl group, a substituted
or unsubstituted cycloalkyl group, a substituted or unsubstituted
aralkyl group, or a hydrogen atom; R.sup.22 represents a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted aralkyl group, or a hydrogen
atom; and R.sup.23 to R.sup.25 independently represent a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted cycloalkyl group, a substituted or unsubstituted
alkoxyl group, a hydrogen atom, or a halogen atom.
The color filter of the present invention can be fabricated, as one
example, by dissolving beforehand the dye of the present invention
(red, green or blue) in a photosensitive resin composition, forming
the resulting formulation into a film on a substrate by casting,
spin coating or the like and then patterning the film by exposure
to light. Alternatively, at least two kinds of dyes of the present
invention can be mixed to obtain a red, green or blue color.
With reference to the accompanying drawings, a typical filter
fabrication process will hereinafter be described taking the
fabrication of a stripe filter as one example.
First, one of the dyes (red, green or blue) according to this
invention is dissolved in a solvent containing photosensitive resin
at a proportion of 1-100 parts by weight, preferably 40-100 parts
by weight in 100 parts by weight of a photosensitive resin, and the
resulting formulation is spin-coated on a substrate 1 by using a
spinner (FIG. 3). The thickness of a resist layer 2 is usually
0.5-100 .mu.m although it is determined depending on spectroscopic
characteristics desired. After the resist layer 2 is dried, the
resist layer 2 is pre-baked under suitable temperature conditions.
The resist layer is exposed to light or an electron beam, to which
the resist has sensitivity, through a mask 3 having a desired
pattern corresponding to a pattern to be formed-(e.g., a stripe
pattern)-FIG. 4. The resist layer so exposed is then developed to
form a pattern 4 (FIG. 5). Finally, post-baking is applied under
appropriate temperature conditions.
To form a color filter having two or more colors, the steps of from
FIG. 3 to FIG. 5 are repeated using dyes corresponding to the
respective colors as needed, namely, as many times as the number of
filter colors employed, thereby making it possible to form, for
example, a color filter having three colored layers 5,6,7 of
different colors as shown in FIG. 6. Where a black matrix is
formed, it is desired to form it before the formation of colored
layers.
As has been described above, patterning of each dye layer can be
conducted on an optically transparent substrate. No particular
limitation is imposed on the substrate to be used, insofar as it
permits patterning of the dye layer and-the color filter so formed
functions as desired.
Examples of the substrate include a glass plate; and films or
plates of resins such as polyvinyl alcohol, hydroxyethylcellulose,
polymethyl methacrylate, polyesters, polybutyral, polyamides,
polyethylene, polyvinyl chloride, polyvinylidene chloride,
polycarbonates, polyolefin copolymers, vinyl chloride copolymers,
vinylidene chloride copolymers and styrene copolymers. A patterned
dye layer can be formed integrally with a substrate which is
applied as a color filter.
The present invention will hereinafter be described in detail by
the following examples. It should however be borne in mind that
this invention should not be limited to or by the following
examples.
EXAMPLE 1
A mixture of ten parts of 1-amino-4-hydroxy-2-chloroanthraquinone,
5 parts of polyvinyl alcohol having an average molecular weight of
750, 5 parts of potassium carbonate and 100 parts of
dimethylformamide was heated to 120.degree. C. and then, reacted
for 10 hours. The reaction mixture was poured into 500 parts of 5%
hydrochloric acid solution, followed by extraction with 100 parts
of chloroform. The extract was purified by column chromatography
(eluent: chloroform-methanol). The purified product (8 parts) and
the compound represented by the following formula (24): ##STR18##
were then reacted. The reaction product was purified by column
chromatography, whereby 7 parts of the compound represented by the
following formula (25): ##STR19## and its isomer were obtained.
EXAMPLE 2
A mixture of 14 parts of 3-nitrophthalonitrile, 10 parts of
polyvinyl alcohol having an average molecular weight of 750, 5
parts of sodium hydride and 200 parts of dimethylformamide was
heated to 120.degree. C. and then, reacted for 10 hours. The
reaction mixture was extracted with 500 parts of chloroform. The
extract was purified by column chromatography (eluent:
chloroform-methanol). The purified product (5 parts), 1 part of
cuprous chloride, 4 parts of diazabicycloundecene and 100 parts of
n-amyl alcohol were mixed, followed by reaction for 6 hours under
reflux. The reaction mixture was concentrated under reduced
pressure to distill off the amyl alcohol. The residue was purified
by column chromatography. The purified product (7 parts) and the
compound represented by the formula (24) were then reacted. The
reaction product was purified by column chromatography, whereby 7
parts of the compound represented by the following formula (26):
##STR20## and its isomer were obtained.
EXAMPLE 3
A mixture of ten parts of 1,4-diamino-2,3-dichloroanthraquinone, 5
parts of polyvinyl alcohol having an average molecular weight of
750, 5 parts of potassium carbonate and 50 parts of
dimethylformamide was heated to 120.degree. C. and then, reacted
for 10 hours. The reaction mixture was poured into 500 parts of 5%
hydrochloric acid solution, followed by extraction with 300 parts
of chloroform. The extract was purified by column chromatography
(eluent: chloroform-methanol). The purified product (5 parts.) and
the compound represented by the formula (24) were then reacted. The
reaction product was purified by column chromatography, whereby 5
parts of the compound represented by the following formula (27):
##STR21## and its isomer were obtained.
EXAMPLE 4
The dye (3.2 parts) of the formula (25) and 80 parts of a 20%
solution of a stilbazole photosensitive resin in polyvinyl alcohol
were mixed. A color filter substrate with black stripes of 20 .mu.m
wide was spincoated to a thickness of 3 .mu.m with the resulting
mixture. After being photomasked, the substrate was exposed to
ultraviolet rays under a halogen lamp. The uncured parts were
washed off, whereby a red filter layer was formed. In a similar
manner, a green and blue filter layers were formed on the same
substrate using dyes represented by the formulas (26) and (27),
respectively.
The thus-obtained filter for a color LCD was free of color mixing
between the individual colors and hence had vivid color tones. In
addition, no quality deterioration was observed although it was
heated to 250.degree. C. during formation of ITO electrodes. The
filter did not undergo deterioration either in a weathering test by
a weatherometer or in a light-resistance test under carbon arc
lamps.
COMPARATIVE EXAMPLE 1
In a similar manner to Example 4, a color filter was fabricated
using "M/P Pink REL" and "PS Green B" (each, trade name; product of
Mitsui Toatsu Dyes, Ltd.) and "Macrolex Blue 2R" (trade name;
product of Bayer A. G.). In Table 1, characteristics of the color
filter are presented in comparison with those of the color filter
fabricated in Example 4.
The following methods and standards were followed for the
measurements of the respective characteristics and for the
evaluation of the measurement results.
1. Transmittance characteristics
A: Maximum transmittance .gtoreq.80% with the proviso that the
transmittance is 10% or lower at (the wavelength for the maximum
transmittance .+-.50 nm).
C: Maximum transmittance .ltoreq.70%, with the proviso that the
transmittance is 10% or lower at (the wavelength for the maximum
transmittance .+-.50) nm.
B: Other than A or C
2. Moistureproofness
Color difference was determined after each filter was stored at 95%
R. H. and 60.degree. C. for 200 hours.
A: .DELTA.E.ltoreq.3
B: 3<.DELTA.E<5
C: .DELTA.E.gtoreq.5
3. Light resistance
Color difference was determined after each filter was exposed to
light with a fadeometer at 60.degree. C. for 200 hours.
A: .DELTA.E.ltoreq.3
B: 3<.DELTA.E<5
C: .DELTA.E.gtoreq.5
4. Heat resistance
Color difference was determined after each filter was stored at
250.degree. C. for 1 hour.
A: .DELTA.E.ltoreq.3
B: 3<.DELTA.E<5
C: .DELTA.E.gtoreq.5
TABLE 1 ______________________________________ Example 4 Comp. Ex.
1 ______________________________________ Migration of dye Not
observed Observed Transmittance characteristics Red A B Green A B
Blue A C Moistureproofness Red A C Green A B Blue A C Light
resistance Red A B Green A B Blue A C Heat resistance Red A C Green
A B Blue A C ______________________________________
EXAMPLE 5
Dissolved in 30 parts of glacial acetic acid were 10 parts of
1-amino-2-p-acetylphenoxy-4-hydroxyanthraquinone and 3.5 parts of
benzaldehyde. Sulfuric acid (2 parts) was added to the resulting
solution, followed by reaction at 40.degree.-45.degree. C. for 12
hours. The reaction mixture was poured into 500 ml of water. The
resulting precipitate was collected by filtration, followed by
drying. The residue was purified by column chromatography, whereby
7 parts of the compound represented by the following formula (28)
were obtained. ##STR22##
Elemental analysis for: C.sub.29 H.sub.19 NO.sub.5
TABLE 2 ______________________________________ C H N
______________________________________ Calculated (%) 75.49 4.12
3.04 Found (%) 75.48 4.13 3.06
______________________________________
EXAMPLE 6
Ten parts of 3-nitrophthalonitrile, 9.4 parts of
p-hydroxyacetophenone and 2.2 parts of 60% sodium hydride were
added to 150 parts of dimethylformamide and heated to 120.degree.
C., followed by reaction for 10 hours. The reaction mixture was
poured into 1000 parts of 5% hydrochloric acid solution, followed
by extraction with 400 parts of chloroform. The resulting extract
was purified by column chromatography (eluent: chloroformmethanol).
The compound so purified (5 parts), 0.5 part of cuprous chloride,
2.7 parts of diazabicycloundecene and 50 parts of n-amyl alcohol
were mixed, followed by reaction for 5 hours under reflux. Amyl
alcohol was distilled off under reduced pressure from the reaction
mixture, followed by purification by column chromatography. Three
parts of the purified product and 0.4 part of benzaldehyde were
reacted at 40.degree.-45.degree. C. for 10 hours in 50 parts of
glacial acetic acid in the presence of sulfuric acid. The reaction
mixture was poured into 500 parts of water. The resulting mixture
was filtered, dried and then purified by column chromatography,
whereby 2 parts of the compound represented by the following
formula (29): ##STR23## and its isomer were obtained.
Elemental analysis for C.sub.92 H.sub.56 N.sub.8 O.sub.8 Cu
TABLE 3 ______________________________________ C H N
______________________________________ Calculated (%) 75.43 3.83
7.65 Found (%) 75.42 3.85 7.63
______________________________________
EXAMPLE 7
A mixture of ten parts of 1,4-diamino-2-chloroantraquinone, 7.5
parts of p-mercaptoacetophenone, 1.2 parts of potassium carbonate
and 50 parts of dimethylformamide was heated to 120.degree. C.,
followed by reaction for 10 hours. The reaction mixture was poured
into 500 parts of 5% hydrochloric acid solution, followed by
extraction with 300 parts of chloroform. The extract was purified
by column chromatography (eluent: chloroform-methanol). Eight parts
of the purified product and 2.8 parts of benzaldehyde were reacted
at 40.degree.-45.degree. C. for 9 hours in 60 parts of glacial
acetic acid in the presence of sulfuric acid. The reaction mixture
was poured into 500 parts of water. The resulting precipitate was
filtered, dried and then purified by column chromatography, whereby
6 parts of the compound represented by the following formula (30):
##STR24##
Elemental analysis for C.sub.29 H.sub.20 N.sub.2 O.sub.3 S
TABLE 4 ______________________________________ C H N
______________________________________ Calculated (%) 73.11 4.20
5.88 Found (%) 73.12 4.22 5.87
______________________________________
EXAMPLE 8
The dye (3.2 parts) of formula (28) and 80 parts of a 20% solution
of the photosensitive resin disclosed in Japanese Patent
Publication No. 15026/1975 were mixed. A color filter substrate
with black stripes of 20 .mu.m wide was spin-coated to a thickness
of 3 .mu.m with the resulting mixture. After being photomasked, the
substrate was exposed to ultraviolet rays under a halogen lamp. The
uncured parts were washed off, whereby a red filter layer was
formed. In a similar manner, a green and blue filter layers were
formed using dyes represented by formula (29) and (30),
respectively.
The thus-obtained filter for a color LCD was free of color mixing
between the individual colors and hence had vivid color tones. In
addition, no quality deterioration was observed although it was
heated to 250.degree. C. during formation of ITO electrodes. The
filter did not undergo deterioration either in a weathering test by
a weatherometer or in a light-resistance test under carbon arc
lamps.
EXAMPLE 9
Fifteen parts of 1-amino-4-hydroxy-2-p-methylphenoxyanthraquinone,
10 parts of N-chloromethyl-ephenylmaleimide and 3 parts of zinc
chloride were added to 80 parts of dichloroethane, followed by
heating under reflux for 7 hours while shielding the reaction
system from light and moisture. The reaction mixture was cooled and
then poured into 1000 parts of methanol. The precipitated solid was
collected by filtration and then dried, whereby 7 parts of the
compound represented by the following formula (31): ##STR25## were
obtained.
Elemental analysis for C.sub.32 H.sub.22 N.sub.2 O.sub.6 :
TABLE 5 ______________________________________ C H N
______________________________________ Calculated (%) 72.45 4.15
5.28 Found (%) 72.43 4.20 5.29
______________________________________
EXAMPLE 10
After 15 parts of
1,4-diamino-2-p-hydroxyethylphenylthioanthraquinone were converted
to the sodium oxide with sodium hydride, it was reacted at
70.degree. C. for 4 hours in a mixture consisting of 4.5 parts of
acrylic chloride and 50 parts of pyridine. The reaction mixture was
poured into 500 parts of water. The precipitated solid was
collected by filtration and then dried. By chromatographic
purification on a column, were obtained 10 parts of the compound
represented by the following formula (32): ##STR26##
Elemental analysis for C.sub.25 H.sub.20 N.sub.2 O.sub.4 S:
TABLE 6 ______________________________________ C H N
______________________________________ Calculated (%) 67.57 4.51
6.31 Found (%) 67.59 4.55 6.33
______________________________________
EXAMPLE 11
Twenty parts of
1-amino-2-p-hydroxyethylphenoxy-4-hydroxyanthraquinone were
dissolved in 60 parts of pyridine, followed by the dropwise
addition of 11 parts of benzenesulfonyl chloride at 5.degree. C.
After they were reacted at 0.degree.-5.degree. C. for 20 hours, the
reaction mixture was poured into 1000 parts of water. The
precipitated solid was collected by filtration and dried, whereby
22 parts of a sulfonate ester were obtained. The sulfonate ester
(20 parts) was added to 80 parts of picoline, followed by reaction
at 85.degree. C. for 6 hours. The reaction mixture was concentrated
in an evaporator so that 25 parts of the quaternary ammonium salt
were obtained.
Twenty parts of the quaternary ammonium salt thus obtained, 4 parts
of benzaldehyde and 7 parts of piperidine were added to 50 parts of
methanol, followed by reaction at 45.degree. C. for 200 hours under
shade. The reaction mixture was added dropwise to 1000 parts of
diethyl ether to precipitate a solid. The solid was collected by
filtration and then dried, whereby 18 parts of the compound
represented by the following formula (33) were obtained:
##STR27##
Elemental analysis for C.sub.41 H.sub.32 N.sub.2 O.sub.7 S
TABLE 7 ______________________________________ C H N
______________________________________ Calculated (%) 70.69 4.60
4.02 Found (%) 70.70 4.65 4.08
______________________________________
EXAMPLES 12-49
The compounds (D-A-Y) shown in Table 8 were synthesized likewise-.
Each of color filters fabricated by using the compounds shown in
Table 8 was free from color mixing between the colors and had vivid
color tone. In addition, no quality deterioration was observed
although they were heated to 250.degree. C. during formation of ITO
electrodes. Those filter did not undergo deterioration either in a
weathering test by a weatherometer or in a light-resistance test
under carbon arc lamps. Incidentally, each .lambda.max was measured
in N,N-dimethylformamide.
TABLE 8 - D(AYn.sup.1)n.sup.2 (1) Compd. .lambda. max No. D A Y
n.sup.1 n.sup.2 (nm) 34 ##STR28## (CH.sub.2 ).sub.2 ##STR29## 1 1
511 35 ##STR30## (CH.sub.2 ).sub.2 ##STR31## 1 1 510 36 ##STR32##
(CH.sub.2 ).sub.2 ##STR33## 1 1 515 37 ##STR34## None ##STR35## 1 1
511 38 ##STR36## None ##STR37## 1 1 530 39 ##STR38## (CH.sub.2
).sub.2 ##STR39## 1 1 528 40 ##STR40## ##STR41## ##STR42## 1 1 510
41 ##STR43## CH.sub.2 ##STR44## 1 1 508 42 ##STR45## CH.sub.2
##STR46## 1 1 509 43 ##STR47## None ##STR48## 1 1 558 44 ##STR49##
None ##STR50## 1 1 560 45 ##STR51## None ##STR52## 1 1 559 46
##STR53## CH.sub.2 ##STR54## 1 1 561 47 ##STR55## None ##STR56## 1
1 550 48 ##STR57## None ##STR58## 1 2 550 49 ##STR59## CH.sub.2
##STR60## 1 1 551 50 ##STR61## (CH.sub.2 ).sub.2 ##STR62## 1 1 550
51 ##STR63## (CH.sub.2 ).sub.2 ##STR64## 1 2 551 52 ##STR65## None
##STR66## 1 2 575 53 ##STR67## O ##STR68## 1 4 697 54 ##STR69##
CH.sub.2 ##STR70## 1 4 699 55 ##STR71## ##STR72## ##STR73## 1 4 698
56 ##STR74## CH.sub.2 ##STR75## 1 4 720 57 ##STR76## CH.sub.2
##STR77## 1 4 720 58 ##STR78## CH.sub.2 ##STR79## 1 4 685 59
##STR80## CH.sub.2 ##STR81## 1 4 710 60 ##STR82## None ##STR83## 1
1 448 61 ##STR84## CH.sub.2 ##STR85## 1 1 450 62 ##STR86## CH.sub.2
##STR87## 1 1 451 63 ##STR88## None ##STR89## 1 1 447 64 ##STR90##
None ##STR91## 1 1 451 65 ##STR92## CH.sub.2 ##STR93## 1 2 663 66
##STR94## None ##STR95## 1 2 680 67 ##STR96## CH.sub.2 ##STR97## 1
1 580 68 ##STR98## None ##STR99## 1 1 460 69 ##STR100## CH.sub.2
##STR101## 1 1 585 70 ##STR102## None ##STR103## 1 1 583 71
##STR104## CH.sub.2 ##STR105## 1 1 584
EXAMPLE 50
After 20 parts of 1,4-diamino-2-p-hydroxyphenylthioanthraquinone
were converted to the sodium oxide with sodium hydride, it was
reacted at 70.degree. C. for 3 hours in a mixture consisting of 5.5
parts of terephthaloyl dichloride and 90 parts of pyridine. The
reaction mixture was poured into 500 parts of an aqueous methanol
solution. The precipitated solid was collected by filtration and
then dried. By chromatographic purification on a column, were
obtained 13 parts of the compound represented by the following
formula (72): ##STR106##
Elemental analysis for C.sub.48 H.sub.30 N.sub.4 O.sub.8 S.sub.2
(Mw: 854)
TABLE 9 ______________________________________ C H N
______________________________________ Calculated (%) 67.45 3.51
6.56 Found (%) 67.48 3.59 6.53
______________________________________
EXAMPLE 51
After 20 parts of
1-amino-2-p-hydroxyethylphenoxy-4-hydroxyanthraquinone were
converted to the sodium oxide with sodium hydride, it was reacted
at 70.degree. C. for 3 hours in a mixture consisting of 4.9 parts
of terephthaloyl dichloride and 90 parts of pyridine. The
reaction-mixture was poured into 500 parts of an aqueous methanol
solution. The precipitated solid was collected by filtration and
then dried. By chromatographic purification on a column, were
obtained 8 parts of the compound represented by the following
formula (73): ##STR107##
Elemental analysis for C.sub.52 H.sub.36 N.sub.2 O.sub.12 (Mw:
880)
TABLE 10 ______________________________________ C H N
______________________________________ Calculated (%) 70.91 4.09
3.18 Found (%) 70.95 4.18 3.16
______________________________________
EXAMPLE 52
Ten parts of 3-nitrophthalonitrile, 18 parts of ethylene glycol and
2.3 parts of 60% sodium hydride were added to 150 parts of
dimethylformamide and heated to 120.degree. C., followed by
reaction for 10 hours. The reaction mixture was poured into 1000
parts of 5% hydrochloric acid solution, followed by extraction with
400 parts of chloroform. The resulting extract was purified by
column chromatography (eluent: chloroformmethanol). The compound so
purified (5 parts), 0.7 part of cuprous chloride, 4 parts of
diazabicycloundecene and 50 parts of n-amyl alcohol were mixed,
followed by reaction for 5 hours under reflux. Amyl alcohol was
distilled off under reduced pressure from the reaction mixture,
followed by purification by column chromatography. Three parts of
the purified product and 2.3 part of benzoic chloride were reacted
at 70.degree. C. for 3 hours in 30 parts of pyridine. The reaction
mixture was poured into 500 parts of water. The resulting
precipitate was collected by filtration, dried and then purified by
column chromatography, whereby 2.5 parts of the compound
represented by the following formula (74) were obtained:
##STR108##
Elemental analysis for C.sub.68 H.sub.48 N.sub.8 O.sub.12 Cu (Mw:
864)
TABLE 11 ______________________________________ C H N
______________________________________ Calculated (%) 66.26 3.90
9.09 Found (%) 66.23 3.95 9.11
______________________________________
EXAMPLE 53
The dye (3.2 parts) of the formula (72) and 80 parts of a 20%
solution of a stilbazole photosensitive resin in polyvinyl alcohol
were mixed. A color filter substrate with black stripes of 20 .mu.m
wide was spin-coated to a thickness of 3 .mu.m with the resulting
mixture. After photomasked, the substrate was exposed to
ultraviolet rays under a halogen lamp. The uncured parts were
washed off, whereby a blue filter layer was formed. In a similar
manner, red and green filter layers were formed using the compound
(73) and the compound (74), respectively.
The thus-obtained filter for a color LCD was free of color mixing
between the individual colors and hence had vivid color tones. In
addition, no quality deterioration was observed although it was
heated to 250.degree. C. during formation of ITO electrodes. The
filter did not undergo deterioration either in a weathering test by
a weatherometer or in a light-resistance test under carbon arc
lamps.
In Table 12, characteristics of the color filter fabricated in
Example 53 are presented in comparison with those of the color
filter fabricated in Comparative Example 1.
TABLE 12 ______________________________________ Example 53 Comp.
Ex. 1 ______________________________________ Dye migration Not
observed Observed Transmittance characteristics Red A B Green A B
Blue A C Moistureproofness Red A C Green A B Blue A C Light
resistance Red A B Green A B Blue A C Heat resistance Red A C Green
A B Blue A C ______________________________________
EXAMPLE 54
Fifteen parts of 1,4-diamino-2,3-dichloroantraquinone, 13 parts of
p-dibutylaminophenol, 8.1 parts of potassium carbonate and 70 parts
of dimethylformamide were reacted at 120.degree. C. for 10 hours.
The reaction mixture was poured into 500 parts of 5% hydrochloric
acid solution, followed by extraction with 300 parts of chloroform.
The extract was purified by column chromatography (eluent:
chloroform-methanol), whereby 9 parts of the compound represented
by the following formula (75) were obtained: ##STR109##
Elemental analysis for C.sub.42 H.sub.52 N.sub.4 O.sub.4 (Mw:
676)
TABLE 13 ______________________________________ C H N
______________________________________ Calculated (%) 74.56 7.69
8.28 Found (%) 74.53 7.75 8.31
______________________________________
EXAMPLE 55
Fifteen parts of the below-described compound having the formula
(76) were converted to the acid chloride with thionyl chloride in
toluene, followed by reaction with 15 parts of ditolylamine at
90.degree. C. for 4 hours. After the reaction mixture was
concentrated in an evaporator, the residue was purified by column
chromatography, thereby 10 parts of the compound represented by the
following formula (77) were obtained. ##STR110##
Elemental analysis for C.sub.37 H.sub.30 N.sub.2 O.sub.5 (Mw:
582)
TABLE 14 ______________________________________ C H N
______________________________________ Calculated (%) 76.29 5.16
4.81 Found (%) 76.31 5.22 4.83
______________________________________
EXAMPLE 56
3 Parts of the dye of formula (75) and 30 parts of "SD-17" (product
of Dainippon Ink & Chemicals, Inc.) were mixed. A color filter
substrate with black stripes of 20 .mu.m wide was spin-coated to a
thickness of 3 .mu.m with the resulting mixture. After being
photomasked, the substrate was exposed to ultraviolet rays under a
halogen lamp. The uncured parts were washed off, whereby a blue
filter layer was formed. In a similar manner, a red filter layer
was formed using the compound (77).
The thus-fabricated filter was free of color mixing between the
individual colors and hence had vivid color tones. In addition, no
quality deterioration was observed although it was heated to
250.degree. C. during formation of ITO electrodes. The filter did
not undergo deterioration either in a weathering test by a
weatherometer or in a light-resistance test under carbon arc
lamps.
EXAMPLES 57-101
The compounds (D-E-D) shown in Table 15 were synthesized in a
similar manner to Examples 51-52. The compounds (D-B-Z) represented
in Table 16 were synthesized in a similar manner to Examples 54-55.
Each of color filters fabricated by using the compounds was free
from color mixing between the colors and had vivid color tone. In
addition, no quality deterioration was observed although they were
heated to 250.degree. C. during formation of ITC electrodes. Those
filter did not undergo deterioration either in a weathering test by
a weatherometer or in a light-resistance test under carbon arc
lamps. Incidentally, each .lambda..sub.max was measured in
toluene.
TABLE 15
__________________________________________________________________________
Compd. No. D E .lambda.max
__________________________________________________________________________
(nm) 78 ##STR111## ##STR112## 510 79 ##STR113## ##STR114## 511 80
##STR115## ##STR116## 512 81 ##STR117## ##STR118## 509 82
##STR119## ##STR120## 531 83 ##STR121## ##STR122## 530 84
##STR123## ##STR124## 529 85 ##STR125## ##STR126## 532 86
##STR127## ##STR128## 513 87 ##STR129## ##STR130## 512 88
##STR131## ##STR132## 530 89 ##STR133## ##STR134## 533 90
##STR135## ##STR136## 449 91 ##STR137## ##STR138## 450 92
##STR139## ##STR140## 451 93 ##STR141## ##STR142## 613 94
##STR143## CH.sub.2 611 95 ##STR144## ##STR145## 581 96 ##STR146##
##STR147## 580 97 ##STR148## ##STR149## 699 98 ##STR150## CH.sub.2
698
__________________________________________________________________________
TABLE 16
__________________________________________________________________________
D(BZ).sub.m Compd. .lambda.max No. D B Z m (nm)
__________________________________________________________________________
99 ##STR151## None ##STR152## 1 449 100 ##STR153## CH.sub.2
##STR154## 4 699 101 ##STR155## CH.sub.2 ##STR156## 4 698 102
##STR157## None ##STR158## 4 698 103 ##STR159## CH.sub.2 ##STR160##
4 722 104 ##STR161## None ##STR162## 4 720 105 ##STR163## None
##STR164## 4 693 106 ##STR165## CH.sub.2 ##STR166## 4 694 107
##STR167## CH.sub.2 ##STR168## 4 710 108 ##STR169## None ##STR170##
2 660 109 ##STR171## None ##STR172## 1 460 110 ##STR173## None
##STR174## 2 543 111 ##STR175## ##STR176## 1 510 112 ##STR177##
##STR178## 1 512 113 ##STR179## ##STR180## 1 510 114 ##STR181##
None ##STR182## 1 511 115 ##STR183## None ##STR184## 1 531 116
##STR185## None ##STR186## 1 530 117 ##STR187## None ##STR188## 1
551 118 ##STR189## None ##STR190## 2 550 119 ##STR191## None
##STR192## 2 549 120 ##STR193## None ##STR194## 1 580 121
##STR195## None ##STR196## 1 448 122 ##STR197## None ##STR198## 1
447
__________________________________________________________________________
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